Iron Phosphorus Clusters with N-Heterocyclic Carbene Ligation

doi:10.6023/A24060203

Abstract

Three iron phosphorus clusters with N-heterocyclic carbene ligation have been synthesized from the reactions of low-coordinate iron(0) complexes [(NHC)Fe(η²:η²-dvtms)] (NHC = N-heterocyclic carbene; dvtms = divinyltetramethylisiloxane) with white phosphorus and have been characterized by spectroscopic methods. The iron phosphorus clusters [(IMes)₂Fe₂(μ-η⁵:η⁵-cyclo-P₅)] (1), [(IMes)₃Fe₃(μ-η⁶:η⁶:η⁶-P₉)] (2) and [(IMes)₂Fe₂(μ-η²:η²-cyclo-P₄P(IMes))(μ-η³:η³-P₃)] (3) were isolated from the equimolar reaction of [(IMes)Fe(η²:η²-dvtms)] (IMes = 1,3-dimesitylimidazol-2-ylidene) with P₄ at low temperature (-30 ℃ to room temperature) upon recrystallization. Complexes 1 and 3 can be synthesized in 18% and 32% isolated yields, respectively, from the reactions of [(IMes)Fe(η²:η²-dvtms)] with P₄ at different reaction temperature (80 ℃ and -30 ℃ to room temperature, respectively). Complex 2 can only be obtained in trace amount from the low-temperature reaction. The three iron phosphorus clusters 1-3 have been characterized by single-crystal X-ray diffraction studies. Complex 1 shows an anti-sandwich type structure with the Fe···Fe distance of 2.515(1) Å and the μ-η⁵:η⁵-P₅ligand in disorder. Analogous complex [(IDep)₂Fe₂(μ-η⁵:η⁵-P₅)] (4, IDep = 1,3-di(2’,6’-diethylphenyl)imidazol-2-ylidene) can be synthesized from the reaction of [(IDep)Fe(η²:η²-dvtms)] with P₄. Its molecular structure established by X-ray diffraction study does not exhibit disorder in the μ-η⁵:η⁵-P₅ ligand and the two iron centers show nearly identical coordination environment. The zero-field ⁵⁷Fe Mössbauer spectrum of 1 measured at 80 K shows a quadrupole doublet with the isomer shift δ = 0.32 mm•s^-1 and quadrupole splitting |ΔE_Q| = 0.61 mm•s^-1. Magnetic susceptibility measurements point out a doublet state (S=1/2) for 1. The characterization data suggests that 1 and 4 can be described as the III-type mixed valence complex based on the Robin-Day Models. Complex 2 represents the first example of metal complexes featuring a P₉ligand. The polyphosphide ligand contains two paralleling P₃ triangles and three boat-shaped P₆ faces. Each P₆ face is coordinating with a Fe(IMes) fragment in η⁶-fashion. The three Fe atoms form a Fe₃ triangle with the Fe···Fe distances close to each other (2.626(1) Å in average). Complex 3 features a μ-η²:η²-cyclo-P₄P(IMes) ligand and a μ-η³:η³-P₃ ligand. The bond distances and angles of the two polyphosphide ligands in 3 are close to those of the counterparts in [(IMes)₂Co₂(μ-η²:η²-cyclo-P₄P(iPr₂Im))(μ-η³:η³-P₃)]. The ¹H and ³¹P NMR spectra of 3 are indicative of its diamagnetic nature. The ⁵⁷Fe Mössbauer quadrupole doublet of 3 measured at 80 K has a isomer shift δ = 0.26 mm•s^-1 and quadrupole splitting |ΔE_Q| = 0.91 mm•s^-1.

Key words: N-heterocyclic carbene, iron, white phosphorus, cluster compounds, polyphosphide

Cite this article

Du Mu, Yang Chengbo, Chen Qi, Deng Liang. Iron Phosphorus Clusters with N-Heterocyclic Carbene Ligation[J]. Acta Chimica Sinica, doi: 10.6023/A24060203.

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氮杂环卡宾配位的铁磷簇合物